CN112121737B - Preparation method of antibacterial phase-change energy-storage microcapsule and fiber - Google Patents
Preparation method of antibacterial phase-change energy-storage microcapsule and fiber Download PDFInfo
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- CN112121737B CN112121737B CN202011014261.0A CN202011014261A CN112121737B CN 112121737 B CN112121737 B CN 112121737B CN 202011014261 A CN202011014261 A CN 202011014261A CN 112121737 B CN112121737 B CN 112121737B
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- change energy
- microcapsule
- tertiary amine
- energy storage
- antibacterial
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 62
- 238000004146 energy storage Methods 0.000 title claims abstract description 53
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 49
- 239000000835 fiber Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 32
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 239000011232 storage material Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 8
- 230000008859 change Effects 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 13
- -1 quaternary ammonium halogen Chemical class 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 7
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 4
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 claims description 4
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZFQTXVDBSYNXDE-UHFFFAOYSA-N n'-(2-aminoethyl)-n'-methylpropane-1,3-diamine Chemical compound NCCN(C)CCCN ZFQTXVDBSYNXDE-UHFFFAOYSA-N 0.000 claims description 4
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 claims description 4
- OMKZWUPRGQMQJC-UHFFFAOYSA-N n'-[3-(dimethylamino)propyl]propane-1,3-diamine Chemical compound CN(C)CCCNCCCN OMKZWUPRGQMQJC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 3
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 3
- 229940089456 isopropyl stearate Drugs 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- ZPWFUIUNWDIYCJ-UHFFFAOYSA-N propan-2-yl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(C)C ZPWFUIUNWDIYCJ-UHFFFAOYSA-N 0.000 claims description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- 125000001302 tertiary amino group Chemical group 0.000 abstract description 5
- 238000005956 quaternization reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000012209 synthetic fiber Substances 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000002074 melt spinning Methods 0.000 description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- HYSQEYLBJYFNMH-UHFFFAOYSA-N n'-(2-aminoethyl)-n'-methylethane-1,2-diamine Chemical compound NCCN(C)CCN HYSQEYLBJYFNMH-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Plant Pathology (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract
The invention belongs to the field of synthetic fibers, and particularly relates to a preparation method of an antibacterial phase-change energy-storage microcapsule and a fiber, wherein 1,3, 5-benzene trimethyl acyl chloride and a phase-change energy-storage material are emulsified into emulsion, then are subjected to a cross-linking reaction with a tertiary amine-containing polyamino compound to obtain a microcapsule with a tertiary amine functional group on the surface, and then are reacted with a halogen-containing quaternization reagent to obtain the quaternization phase-change energy-storage microcapsule with better antibacterial performance. The antibacterial phase-change energy-storage microcapsule is applied to fibers, and the obtained fibers have the performances of antibiosis and good washability.
Description
Technical Field
The invention belongs to the field of synthetic fibers, and relates to a preparation method of an antibacterial phase-change energy-storage microcapsule and a fiber.
Background
In the current society, energy is more and more tense, and the consciousness of saving energy is more and more high, and the phase change energy storage microcapsule is a micron-sized material of which the shell is a cross-linked polymer and the core contains a phase change energy storage material, can be applied to fibers, and a textile formed by spinning has the effects of cooling when the temperature is high and preserving heat when the temperature is low. There are many technical reports on the preparation method of the phase change energy storage microcapsule.
Various bacteria and viruses are ubiquitous in life, and the health of a human body is greatly influenced. Fabrics with effective antibacterial properties are becoming more popular, and there are many published reports on the preparation of antibacterial fibers or antibacterial fabrics.
CN1607270A discloses a nano-antibacterial intelligent heat storage fiber, which is prepared by adding antibacterial intelligent heat storage functional powder into fiber, but does not specifically disclose antibacterial intelligent heat storage functional powder; CN103340480A discloses a phase change energy storage cashmere blended knitted underwear, which is prepared by firstly obtaining energy storage blended yarns and then adsorbing chitin modified derivatives on the surfaces of the energy storage blended yarns to obtain antibacterial performance; CN103726125B discloses an anti-mite and antibacterial polyester staple fiber and a preparation method thereof, wherein micron-sized heat-storage anti-mite ceramic powder and silver-loaded nano titanium dioxide composite antibacterial powder are added. With the development of functional materials, people increasingly expect that one functional material can integrate more functions.
The inventor finds a preparation method of the antibacterial phase-change energy-storage microcapsule through a large number of experiments, and the obtained microcapsule can enable the fiber to have the functions of resisting bacteria and storing phase-change energy when being added into the fiber.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an antibacterial phase-change energy-storage microcapsule.
It is another object of the present invention to provide a fiber.
The technical scheme of the invention is as follows:
a preparation method of an antibacterial phase-change energy-storage microcapsule comprises the following steps,
s1, mixing 1,3, 5-benzene trimethyl acyl chloride, a phase change energy storage material and an emulsifier, heating to form liquid, and adding deionized water with the same temperature under high-speed stirring to form emulsion. The emulsifier used in the present application may be a nonionic emulsifier or an anionic emulsifier, or a mixture of a nonionic emulsifier and an anionic emulsifier; the use of a mixture of a non-ionic emulsifier, such as OP-10, and an anionic emulsifier, such as sodium dodecylbenzenesulfonate, enables better stability of the resulting emulsion due to steric and electrostatic repulsion effects. The high-speed stirring speed is not particularly limited as long as a stable emulsion can be formed, and may preferably be 800 to 2000 rpm.
S2, adding a polyamino compound containing tertiary amine into the emulsion obtained in the step S1, stirring for 0.5-3 hours, separating and washing with water to obtain a tertiary amine modified microcapsule; the tertiary amine-containing polyamino compound contains at least one primary amino group, at least one secondary amino group and at least one tertiary amino group in a molecule or contains at least two primary amino groups and at least one tertiary amino group in a molecule;
s3, dispersing the tertiary amine modified microcapsule obtained in the step S2 in an organic solvent, adding a halogen-containing quaternization agent, heating to 40-60 ℃, stirring for 4-10 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase-change energy storage microcapsule. The organic solvent is a polar organic solvent, and can be selected from tetrahydrofuran, acetone, isopropanol, absolute ethyl alcohol, methanol or ethyl acetate, butyl acetate or methyl ethyl ketone.
In a further scheme, in step S1, the phase change energy storage material is at least one selected from n-docosane, n-eicosane, paraffin, n-hexadecane, n-octadecane, methyl stearate, ethyl stearate, isopropyl stearate and butyl stearate.
In a further scheme, the weight ratio of the 1,3, 5-benzene tricarboxychloride, the phase change energy storage material, the emulsifier and the water in the step S1 is 0.5-1.2: 10: 0.5-1.5: 12-30.
In a further scheme, the heating temperature in the step S1 is higher than the melting point of the phase change energy storage material under normal pressure by more than 5 ℃, but the heating temperature is not higher than 80 ℃.
In a further embodiment, the tertiary amine-containing polyamino compound of step S2 is selected from at least one of N, N-dimethyl dipropylenetriamine, 2, 3-diamino-N-methyl-ethylpropylamine, 2' -diamino-N-methyldiethylamine, and N- (3-aminopropyl) -N-methyl-1, 3-propanediamine.
In a further scheme, the weight ratio of the emulsion to the tertiary amine-containing polyamino compound in the step S2 is 10: 0.1-1.
In a further embodiment, in step S3, the quaternary ammonium agent containing halogen is at least one selected from epichlorohydrin, ethyl chloroacetate, ethyl bromoacetate, chlorooctadecane, bromooctadecane and chlorohexadecane.
In a further embodiment, the weight ratio of the tertiary amine modified microcapsule and the halogen-containing quaternizing agent in step S3 is 1:0.01 to 0.1.
A fiber comprising the antibacterial phase change energy storage microcapsule obtained by the preparation method of any one of the above embodiments.
In a further aspect, the host polymer of the fiber is selected from at least one of polypropylene, polyethylene, polyester, polyamide, polyimide, PVC, and polyacrylonitrile.
The beneficial effects of the invention are:
(1) according to the invention, a tertiary amine-containing polyamino compound is added when the phase change microcapsule is formed, so that the phase change microcapsule can be subjected to a crosslinking reaction with 1,3, 5-benzene tricarboxychloride to form a compact and rigid crosslinking microcapsule shell, and tertiary amine functional groups can be introduced to the surface of the microcapsule shell; the tertiary amine functional group and the quaternary ammonium agent containing halogen are subjected to quaternization reaction, and quaternary ammonium salt with good antibacterial property is generated on the surface of the microcapsule, so that the microcapsule with the surface containing the quaternary ammonium salt functional group and the core containing the phase change energy storage material is obtained, and the antibacterial property and the phase change energy storage property are simultaneously obtained on one material. The preparation method is simple and has strong practicability.
(2) The antibacterial phase-change microcapsule disclosed by the invention is applied to fibers, so that the fibers can be endowed with good antibacterial property and energy storage performance, and the microcapsule is dispersed in a fiber polymer, so that the microcapsule has good washability, and still has good antibacterial performance after being washed for 40 times.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Unless otherwise specified, the parts in the following embodiments are parts by weight.
Detailed description of the preferred embodiments
A preparation method of an antibacterial phase-change energy-storage microcapsule comprises the following steps,
s1, mixing 1,3, 5-benzene trimethyl acyl chloride, a phase change energy storage material and an emulsifier, heating to form liquid, and adding deionized water with the same temperature under high-speed stirring to form emulsion. The emulsifier is a composition of OP-10 and sodium dodecyl benzene sulfonate; the high-speed stirring rotating speed is 800-2000 rpm.
S2, adding a polyamino compound containing tertiary amine into the emulsion obtained in the step S1, stirring for 0.5-3 hours, separating and washing with water to obtain a tertiary amine modified microcapsule; the tertiary amine-containing polyamino compound contains at least one primary amino group, at least one secondary amino group and at least one tertiary amino group in a molecule or contains at least two primary amino groups and at least one tertiary amino group in a molecule;
s3, dispersing the tertiary amine modified microcapsule obtained in the step S2 in an organic solvent, adding a quaternary ammonium agent containing halogen, heating to 40-60 ℃, stirring for 4-10 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule. The organic solvent is selected from tetrahydrofuran, acetone, isopropanol, absolute ethyl alcohol, methanol or ethyl acetate, butyl acetate or methyl ethyl ketone.
In this embodiment, the phase change energy storage material in step S1 is at least one selected from the group consisting of n-docosane, n-eicosane, paraffin, n-hexadecane, n-octadecane, methyl stearate, ethyl stearate, isopropyl stearate, and butyl stearate.
In this embodiment, the weight ratio of the 1,3, 5-benzenetricarboxylic acid chloride, the phase change energy storage material, the emulsifier and the water in step S1 is 0.5-1.2: 10: 0.5-1.5: 12-30.
In the present embodiment, the heating temperature in step S1 is 5 ℃ or higher than the melting point of the phase change energy storage material at normal pressure, but the heating temperature is not more than 80 ℃.
In this embodiment, the tertiary amine-containing polyamino compound in step S2 is selected from at least one of N, N-dimethyldipropylenetriamine, 2, 3-diamino-N-methyl-ethylpropylamine, 2' -diamino-N-methyldiethylamine, and N- (3-aminopropyl) -N-methyl-1, 3-propanediamine.
In this embodiment, the weight ratio of the emulsion to the tertiary amine-containing polyamino compound in step S2 is 10:0.1 to 1.
In this embodiment, the halogen-containing quaternizing agent in step S3 is selected from at least one of epichlorohydrin, ethyl chloroacetate, ethyl bromoacetate, chlorooctadecane, bromooctadecane, and chlorohexadecane.
In this embodiment, the weight ratio of the tertiary amine-modified microcapsule and the halogen-containing quaternizing agent in step S3 is 1:0.01 to 0.1.
A fiber, comprising the antibacterial phase-change energy-storage microcapsule obtained by the preparation method of any of the above embodiments.
In this embodiment, the host polymer of the fiber is selected from at least one of polypropylene, polyethylene, polyester, polyamide, polyimide, PVC, and polyacrylonitrile.
Example 1
0.5 part of 1,3, 5-benzene tricarbochloride, 10 parts of n-docosane, 0.4 part of OP-10 and 0.1 part of sodium dodecyl benzene sulfonate are mixed and heated to 52 ℃ to form liquid, and 12 parts of deionized water with the same temperature is added at the stirring speed of 1000-1100 rpm to form emulsion.
Adding 0.23 part of N, N-dimethyl dipropylenetriamine into the obtained emulsion, stirring for 3 hours, separating and washing to obtain a tertiary amine modified microcapsule;
dispersing 1 part of the obtained tertiary amine modified microcapsule in 50 parts of tetrahydrofuran, adding 0.01 part of epoxy chloropropane, heating to 45 ℃, stirring for 8 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule, which is marked as E-1 and has the average particle size of 3.5 mu m.
Example 2
Mixing 0.9 part of 1,3, 5-benzene trimethyl acyl chloride, 10 parts of butyl stearate, 0.8 part of OP-10 and 0.2 part of sodium dodecyl benzene sulfonate, heating to 30 ℃ to form liquid, and adding 20 parts of deionized water with the same temperature at the stirring speed of 900-1000 rpm to form emulsion.
Adding 1 part of 2, 3-diamino-N-methyl-ethyl propylamine into the obtained emulsion, stirring for 1 hour, separating and washing with water to obtain a tertiary amine modified microcapsule;
dispersing 1 part of the obtained tertiary amine modified microcapsule in 50 parts of methanol, adding 0.05 part of ethyl chloroacetate, heating to 42 ℃, stirring for 6 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule, which is marked as E-2 and has the average particle size of 2.2 microns.
Example 3
1.2 parts of 1,3, 5-benzene trimethyl acyl chloride, 10 parts of n-eicosane, 1.2 parts of OP-10 and 0.3 part of sodium dodecyl benzene sulfonate are mixed and heated to 45 ℃ to form liquid, and 30 parts of deionized water with the same temperature is added at the stirring speed of 1200-1300 rpm to form emulsion.
Adding 4 parts of 2, 2' -diamino-N-methyl diethylamine into the obtained emulsion, stirring for 0.6 h, separating and washing with water to obtain a tertiary amine modified microcapsule;
dispersing 1 part of the obtained tertiary amine modified microcapsule in 50 parts of butyl acetate, adding 0.1 part of chlorooctadecane, heating to 50 ℃, stirring for 7 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule, which is marked as E-3 and has the average particle size of 1.6 mu m.
Example 4
Mixing 0.8 part of 1,3, 5-benzene trimethyl acyl chloride, 10 parts of n-docosyl, 0.9 part of OP-10 and 0.2 part of sodium dodecyl benzene sulfonate, heating to 60 ℃ to form liquid, and adding 16 parts of deionized water with the same temperature at the stirring speed of 1200-1300 rpm to form emulsion.
Adding 2 parts of N- (3-aminopropyl) -N-methyl-1, 3-propane diamine into the obtained emulsion, stirring for 1.5 hours, separating and washing with water to obtain a tertiary amine modified microcapsule;
dispersing 1 part of the obtained tertiary amine modified microcapsule in 50 parts of methanol, adding 0.06 part of bromooctadecane, heating to 45 ℃, stirring for 5 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule, which is marked as E-4 and has the average particle size of 5.7 mu m.
Example 5
1.1 parts of 1,3, 5-benzene trimethyl acyl chloride, 10 parts of n-eicosane, 0.6 part of OP-10 and 0.1 part of sodium dodecyl benzene sulfonate are mixed and heated to 50 ℃ to form liquid, and 18 parts of deionized water with the same temperature is added at the stirring speed of 1000-1100 rpm to form emulsion.
Adding 1 part of 2, 2' -diamino-N-methyl diethylamine into the obtained emulsion, stirring for 2 hours, separating and washing with water to obtain a tertiary amine modified microcapsule;
dispersing 1 part of the obtained tertiary amine modified microcapsule in 50 parts of tetrahydrofuran, adding 0.06 part of chlorooctadecane, heating to 42 ℃, stirring for 6 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule, which is marked as E-5 and has the average particle size of 4.2 mu m.
Example 6
5 parts of antibacterial phase-change energy storage microcapsule E-1 and 95 parts of polypropylene are mixed, and the fiber 1 is obtained through melt spinning, oiling, stretching, heat setting and cooling.
Example 7
3 parts of antibacterial phase-change energy storage microcapsule E-2 and 97 parts of polypropylene are mixed, and then the fiber 2 is obtained through melt spinning, oiling, stretching, heat setting and cooling.
Example 8
And 5 parts of antibacterial phase-change energy storage microcapsule E-3 and 95 parts of polyester are mixed and subjected to melt spinning to obtain fiber 3.
Example 9
And 3 parts of antibacterial phase-change energy storage microcapsule E-4 and 97 parts of polyester are mixed and subjected to melt spinning to obtain fiber 4.
Example 10
And mixing 5 parts of antibacterial phase-change energy storage microcapsule E-5 and 95 parts of polyethylene, carrying out melt spinning, cooling, stretching, drying and shaping to obtain the fiber 5.
Comparative example 1
5 parts of non-antibacterial phase change energy storage microcapsules and 95 parts of polypropylene are mixed, and then melt spinning, oiling, stretching, heat setting and cooling are carried out to obtain the fiber 6.
Comparative example 2
5 parts of non-antibacterial phase-change energy storage microcapsules and 95 parts of polyester are mixed and subjected to melt spinning to obtain the fiber 7.
Comparative example 3
And 5 parts of non-antibacterial phase change energy storage microcapsules and 95 parts of polyethylene are mixed, subjected to melt spinning, cooled, stretched, dried and shaped to obtain the fiber 8.
The antibacterial performance is tested according to GB 20944.3-2008.
And the antibacterial performance of the fibers 1 to 8 is tested after standard washing for 40 times.
The antibacterial ratios of fibers 1 to 8 are shown in the following table.
TABLE 1% fiber 8 antibacterial Rate/%
Therefore, the antibacterial phase change energy storage microcapsule provided by the invention is applied to fibers, and can obviously improve the antibacterial property of the fibers, so that the fibers have an energy storage function and have good antibacterial property.
The foregoing has shown and described the principles, major features, and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. S1, mixing 1,3, 5-benzene trimethyl acyl chloride, a phase change energy storage material and an emulsifier, heating the mixture to form liquid, and adding deionized water with the same temperature under high-speed stirring to form emulsion;
s2, adding a polyamino compound containing tertiary amine into the emulsion obtained in the step S1, stirring for 0.5-3 hours, separating and washing with water to obtain a tertiary amine modified microcapsule;
the tertiary amine-containing polyamino compound is at least one selected from the group consisting of N, N-dimethyldipropylenetriamine, 2, 3-diamino-N-methyl-ethylpropylamine, 2' -diamino-N-methyldiethylamine, and N- (3-aminopropyl) -N-methyl-1, 3-propanediamine;
s3, dispersing the tertiary amine modified microcapsule obtained in the step S2 in an organic solvent, adding a quaternary ammonium agent containing halogen, heating to 40-60 ℃, stirring for 4-10 hours, cooling, separating, cleaning and drying to obtain the antibacterial phase change energy storage microcapsule.
2. The method according to claim 1, wherein the phase-change energy storage material in step S1 is at least one selected from the group consisting of n-docosane, n-eicosane, paraffin wax, n-hexadecane, n-octadecane, methyl stearate, ethyl stearate, isopropyl stearate, and butyl stearate.
3. The method according to claim 1, wherein the weight ratio of the 1,3, 5-benzenetricarboxylic acid chloride, the phase change energy storage material, the emulsifier and the water in the step S1 is 0.5-1.2: 10: 0.5-1.5: 12-30.
4. The method according to claim 1, wherein the heating temperature in step S1 is 5 ℃ or higher than the melting point of the phase change energy storage material under normal pressure, but the heating temperature is not more than 80 ℃.
5. The method according to claim 1, wherein the weight ratio of the emulsion to the tertiary amine-containing polyamino compound in step S2 is 10:0.1 to 1.
6. The method of claim 1, wherein the quaternary ammonium agent containing halogen in step S3 is at least one selected from the group consisting of epichlorohydrin, ethyl chloroacetate, ethyl bromoacetate, chlorooctadecane, bromooctadecane and chlorohexadecane.
7. The method according to claim 1, wherein the weight ratio of the tertiary amine-modified microcapsule to the quaternary ammonium halogen-containing agent in step S3 is 1: 0.01-0.1.
8. A fiber comprising the antibacterial phase-change energy-storage microcapsule obtained by the preparation method according to any one of claims 1 to 7.
9. The fiber of claim 8, the fiber having a host polymer selected from at least one of polypropylene, polyethylene, polyester, polyamide, polyimide, PVC, and polyacrylonitrile.
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